CN107096394A - A kind of high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane and preparation method thereof - Google Patents
A kind of high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane and preparation method thereof Download PDFInfo
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- CN107096394A CN107096394A CN201710230220.7A CN201710230220A CN107096394A CN 107096394 A CN107096394 A CN 107096394A CN 201710230220 A CN201710230220 A CN 201710230220A CN 107096394 A CN107096394 A CN 107096394A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
Abstract
The invention discloses a kind of high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane, it is made up of graphene and proton conductor oxide two-phase, the doping of the graphene is 0.03~0.25wt%, and the content of the proton conductor oxide is 99.75~99.97wt%.In addition, also disclosing the preparation method of above-mentioned high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane.The present invention makes proton conductor oxidation film obtain high electronic conductivity, is significantly improving the H of proton conductor oxidation film by the doping of trace graphite alkene2While permeation flux, the heat endurance and mechanical strength of film are substantially improved, is conducive to the industrialized application of ceramic hydrogen permeation membrane and development.
Description
Technical field
The present invention relates to ceramic material technical field, more particularly to a kind of proton conductor with high osmosis are fine and close
Ceramic hydrogen permeation membrane and preparation method thereof.
Background technology
After the imagination of 19 century 70s " hydrogen economy " is suggested, hydrogen (H2) it is used as a kind of novel energy one
Directly by global extensive concern.Compared with other fossil fuels, hydrogen has many unique advantages as fuel, such as more
High energy density, source are wide, combustion product is water without pollutant emission etc., therefore, (including dolly, public in vehicle
Automobile, truck etc.), airborne vehicle, have a extensive future in terms of the driving such as submarine and steamer and off-network backup battery system.
At present, industrial hydrogen to the mixed gas after gas renormalizing and Coal Gasification mainly by carrying out separating
Arrive.And industrialized isolation technics mainly has pressure-variable adsorption and cryogenic separation two ways, because separation process needs are huge
Energy expenditure and complicated separation equipment, so as to cause high separation costs.In recent ten years, membrane separation technique is due to its separation
Process has that efficiency high, energy consumption be low, equipment is simple and the low advantage of separation costs so that its application in hydrogen separation is received
Increasing concern, the development of embrane method hydrogen isolation technics will bring huge impetus to hydrogen expanding economy.
In membrane separation technique, ceramic of compact hydrogen permeation membrane is compared with organic film, metal film and carbon film etc., due to selectivity
High, acid gas (such as SOx、CO2Deng) corrosivity is more preferably and the advantages of advantage of lower cost, the even more heat as research and development
Point.At present, prior art ceramic of compact hydrogen permeation membrane mainly has two categories below：
(1) single-phase oxide ceramic membrane
Such as the SrCeO of multivalent state ion doping3And BaCeO3Perovskite structure oxide material, has simultaneously at high temperature
Proton and electronic conductivity.Therefore, the dense ceramic membrane prepared using this material has certain through hydrogen capacity at high temperature.
But generally speaking, the electronic conductivity of monophase materialses at the working temperature is very low (being generally less than 0.01S/cm), so as to limit
(when working for 1000 DEG C, thickness is the H of 0.5~1mm film to the through hydrogen capacity of film2Permeation flux is generally below 0.1mLmin-1·cm-2).In order to effectively improve hydrogen permeability, auxiliary external circuit need to be increased to provide electronic conductance, thus do not possess industry still
Application prospect.In addition, cerate material does not possess enough chemically stables still under high temperature (800~1000 DEG C) condition of work
Property, easily with the CO in material gas mixture2And H2O reacts, and causes membrane structure to be destroyed.
(2) two-phase composite ceramic film
In order to the electronic conductivity for improving single phase film it is not enough the problem of, pass through second added with good ionic conductivity
Phase (such as W metal and conductor oxidate SrFeO3), so as to be combined with the oxide composition two-phase with good proton-conducting
Ceramic membrane.Wherein, the second phase Ni introducing can not only greatly improve the electronic conductivity of film, while the machinery that can also improve film is steady
Qualitative and H2Absorption, cracking performance etc., so as to significantly improve the hydrogen permeability of film.Such as the Ni- that thickness is 0.5mm
BaZr0.1Ce0.7Y0.2O3-δPhase membrane, the H at 900 DEG C2Permeation flux can reach 0.25mLmin-1·cm-2.However, at present
Two-phase composite ceramic film remains the technical problem of following two aspects：One is, electronics conduction is mutually aoxidized with proton conductor
Chemical reaction and thermal compatibility problem, especially thermal expansion between thing phase are mismatched, for example, in long-time high temperature operating conditions
Under, Ni may be reacted by diffusion with proton conductor oxide, so as to influence the proton-conducting and stability of film, and then be influenceed
The hydrogen permeability energy of film；Two alternate thermal expansions mismatch (such as 25~900 DEG C, BaZr0.1Ce0.7Y0.2O3-δWith Ni thermal coefficient of expansion
It respectively may be about 9 × 10-6/ DEG C and 16 × 10-6/ DEG C), it can cause film that electronics conduction easily occurs in use and be passed with proton
Lead interphase interface cracking or separate, so as to influence the structural stability and hydrogen permeability energy of film.Two are, existing two-phase composite ceramics
Film is to ensure that electronics conduction is mutually continuous phase, and its addition is up to 35~50vol%, so as to cause phase membrane and single phase film phase
Than proton conduction phase content greatly reduces so that further improve the H of film2Permeance property is restricted, so as to be difficult to reach work
Industry application requirement.In addition, when conducting phase as electronics using W metal, film is carrying out containing SOxAnd CO2Mixed gas separation
When, also there are problems that serious sulfur poisoning and carbon distribution, so as to influence it in the ability of film surface catalytic pyrolysis hydrogen.
The content of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of graphene with high hydrogen permeability
Adulterate proton conductor ceramic of compact hydrogen permeation membrane, by the doping of trace graphite alkene, proton conductor oxidation film is obtained high electricity
Electron conductivity, is significantly improving the H of proton conductor oxidation film2While permeation flux, substantially improve film heat endurance and
Mechanical strength.Another object of the present invention is to provide the preparation side that above-mentioned graphene adulterates proton conductor ceramic of compact hydrogen permeation membrane
Method.
The purpose of the present invention is achieved by the following technical programs：
A kind of high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane that the present invention is provided, by graphene and matter
Sub- conducting oxide two-phase is constituted, and the doping of the graphene is 0.03~0.25wt%, the proton conductor oxide
Content is 99.75~99.97wt%.Preferably, the doping of the graphene is 0.07~0.1wt%, the proton conductor
The content of oxide is 99.90~99.93wt%.
Further, proton conductor oxide of the present invention is perovskite structure composite oxide
BaZr0.1Ce0.7Y0.2O3-δ, or other (600~1000 DEG C) proton conductors oxidations with good proton-conducting at high temperature
Thing material, such as BaZr0.1Ce0.7Yb0.2O3-δDeng.
Another object of the present invention is achieved by the following technical programs：
The preparation method for the above-mentioned high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane that the present invention is provided, with
Graphene or graphene oxide and proton conductor oxide powder are raw material, blended, shaping, dry, high temperature sintering, system
Obtain graphene doping proton conductor ceramic of compact hydrogen permeation membrane.
In such scheme, graphene described in preparation method of the present invention or graphene oxide using dry powder or suspension shape
Formula is added；The thickness of the graphene is that 0.35~1nm, piece footpath are 50~300nm；The thickness of the graphene oxide is 0.7
~1.5nm, piece footpath are 50~300nm；The average grain diameter of the proton conductor oxide powder is 100~300nm.
The present invention can prepare slabbing symmetrical structure film or unsymmetric structure film etc. in terms of node configuration.
Specifically, the present invention prepares sheet symmetrical structure ceramic of compact hydrogen permeation membrane, comprises the following steps：
(1) raw material is mixed with
Using the graphene or graphene oxide and proton conductor oxide powder as raw material, using zirconium oxide ball milling
Machine, using absolute ethyl alcohol, isopropanol or 1-METHYLPYRROLIDONE as decentralized medium, using zirconia ball as mill be situated between, rotating speed 250~
1~3h of ball milling mixing under 300rpm, obtains raw mixture；
(2) it is dry-pressing formed
The raw mixture, which is placed in baking oven at a temperature of 70~80 DEG C, fully to be dried, after disperseing through granulation, using dry
The molded thickness that is pressed under 200~300MPa pressure is 0.4~1mm laminar film green compact；
(3) dry and high temperature sintering
The laminar film green compact carry out high temperature sintering after being dried at a temperature of 80~100 DEG C, obtain the cause of sheet symmetrical structure
Close ceramic hydrogen permeation membrane.
Or, the present invention prepares the fine and close micro-pipe ceramic hydrogen permeation membrane of unsymmetric structure, comprises the following steps：
(1) raw material is mixed with
Using the graphene or graphene oxide and proton conductor oxide powder as raw material, bonding agent polyethers is added
Sulfone, polyethylene of dispersing agent pyrrolidones, using zirconia ball mill, with 1-METHYLPYRROLIDONE, dimethylformamide or diformazan
Sulfoxide is solvent, and zirconia ball is situated between for mill, and 6~12h of ball milling mixing, makes polyether sulfone and polyethylene under 200~300rpm of rotating speed
Pyrrolidones fully dissolves and is well mixed powder material, prepares casting film slurry；Casting film slurry graphene-containing or oxidation
55~64wt% of graphene and proton conductor hopcalite, 28~36wt% of solvent, 7~9wt% of polyether sulfone, polyethylene
0.3~0.5wt% of pyrrolidones；
(2) extruding spinning is molded
The casting film slurry is added into extruding spinning shaped device, 0.5~1h is vacuumized first to remove residual bubbles, so
Obturator liquid afterwards, and by nitrogen pressure and glass rotameter control the core flow velocity that is flowed out from spinneret inner tube for 20~
50mL/min, finally applies 0.3~0.7bar of nitrogen pressure, the casting film slurry is squeezed into the spinning head containing interpolation pipe；From spray
The micro-pipe wet film of silk head extrusion, which is immersed behind 1~4cm the air gap in outer coagulating bath, to be stood after 12~24h gelling solidifications,
Obtain micro-pipe film precursor；
(3) dry and high temperature sintering
The micro-pipe film precursor carries out high temperature sintering after drying, obtains the fine and close micro-pipe ceramic hydrogen permeation of unsymmetric structure
Film.
Further, the sintering condition of high temperature sintering described in preparation method of the present invention is insulation at a temperature of 1350~1500 DEG C
2~5h.
Utilize product made from the preparation method of above-mentioned high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane.
The invention has the advantages that：
(1) doping of the invention by trace graphite alkene, and obtain graphene/saturating hydrogen of proton conductor oxide composite ceramics
Film, electronics conducts phase content (being reduced to below 1.5vol% from 35~50vol%) and adds matter in film is greatly reduced
In the case that son leads phase content, high electronic conductivity (＞ 1S/cm) is obtained, so as to significantly improve proton conductor oxide
The H of film2Permeation flux (reaches 0.32~1.8mLmin-1·cm-2)。
(2) graphene is two-dimensional ultrathin nano material, with fabulous elasticity and pliability, high mechanical strength, this hair
Graphene/proton conductor composite ceramic film that the bright trace graphite alkene big by specific surface area of adulterating is obtained, with excellent heat
Stability and mechanical strength (reaching 36~80MPa), the two-phase thermal expansion of existing biphase ceramics film presence can be avoided to mismatch,
The problems such as membrane structure stability and poor mechanical strength.
(3) present invention utilizes the good catalytic performance of graphene, it is to avoid prior art is generally conducted using Ni as electronics
The serious sulfur poisoning and carbon deposition phenomenon existed during phase, is favorably improved film surface catalytic reaction activity.
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment
Embodiment one：
1st, a kind of high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane of the present embodiment, by graphene and proton
Conductor perovskite structure composite oxide BaZr0.1Ce0.7Y0.2O3-δ(BZCY) two-phase is constituted.Wherein, the doping of graphene is
0.18wt%, BZCY content are 99.82wt%.
2nd, the present embodiment high osmosis graphene adulterate proton conductor ceramic of compact hydrogen permeation membrane preparation method, using concentration as
The BZCY superfine powders that 2mg/mL graphene oxide suspension, average grain diameter are 250nm are raw material.Wherein, the oxidation of use
Graphene film thickness is that 0.7~1.5nm, piece footpath are 50~300nm.Its step is as follows：
(1) raw material is mixed with
Above-mentioned 50mL graphene oxide suspensions and 50g BZCY superfine powders are placed in zirconia ball mill, with anhydrous
Ethanol is that decentralized medium, zirconia ball are that mill is situated between, and ball milling mixing 1h, obtains raw mixture under rotating speed 250rpm；
(2) it is dry-pressing formed
Above-mentioned raw materials mixture is placed in baking oven at a temperature of 70 DEG C and fully dried, after disperseing through granulation, using dry-pressing
It is molded over the laminar film green compact for being pressed into that thickness is 0.75mm under 300MPa pressure；
(3) dry and high temperature sintering
After laminar film green compact dry 2h at a temperature of 80 DEG C, it is sintered using electron tubes type high-temperature electric resistance furnace, sintering condition
For：With 98%N2/ 2%H2Mixed gas is incubated 3h as protection gas at a temperature of 1400 DEG C；Room temperature is naturally cooled to, that is, is obtained
Graphene doping proton conductor (graphene/BaZr0.1Ce0.7Y0.2O3-δ) sheet symmetrical structure ceramic of compact hydrogen permeation membrane.
Embodiment two：
1st, a kind of high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane of the present embodiment, by graphene and proton
Conductor perovskite structure composite oxide BaZr0.1Ce0.7Y0.2O3-δ(BZCY) two-phase is constituted.Wherein, the doping of graphene is
0.09wt%, BZCY content are 99.91wt%.
2nd, the preparation method of the present embodiment high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane, with embodiment
One difference is：The consumption of graphene oxide suspension is 25mL.
Embodiment three：
1st, a kind of high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane of the present embodiment, by graphene and proton
Conductor perovskite structure composite oxide BaZr0.1Ce0.7Y0.2O3-δ(BZCY) two-phase is constituted.Wherein, the doping of graphene is
0.05wt%, BZCY content are 99.95wt%.
2nd, the preparation method of the present embodiment high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane, with embodiment
One difference is：The consumption of graphene oxide suspension is 14mL.
Example IV：
1st, a kind of high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane of the present embodiment, by graphene and proton
Conductor perovskite structure composite oxide BaZr0.1Ce0.7Y0.2O3-δ(BZCY) two-phase is constituted.Wherein, the doping of graphene is
0.10wt%, BZCY content are 99.90wt%.
2nd, the preparation method of the present embodiment high osmosis graphene doping proton conductor ceramic of compact hydrogen permeation membrane, with graphene
Dry powder, average grain diameter are 250nm BaZr0.1Ce0.7Y0.2O3-δ(BZCY) superfine powder is raw material.Wherein, the graphene of use
Piece thickness is that 0.35~1nm, piece footpath are 50~300nm.Its step is as follows：
(1) raw material is mixed with
By above-mentioned 51mg graphenes dry powder, 50g BZCY superfine powders, 6.6g bonding agents polyether sulfone, the poly- second of 0.3g dispersants
Alkene pyrrolidone is placed in zirconia ball mill, and adds 26mLN- methyl pyrrolidones for solvent, and zirconia ball is situated between for mill,
Ball milling mixing 10h under rotating speed 250rpm, makes polyether sulfone and polyvinylpyrrolidone fully dissolve and makes powder material mixing equal
It is even, prepare casting film slurry (graphene-containing and BZCY mixture 59.8wt%, solvent 31.9wt%, polyether sulfone
7.9wt%, polyvinylpyrrolidone 0.36wt%)；
(2) extruding spinning is molded
Above-mentioned casting film slurry is added into extruding spinning shaped device, 1h is vacuumized first to remove residual bubbles, Ran Houtong
Core liquid (water), and control the core flow velocity flowed out from spinneret inner tube to be 50mL/ by nitrogen pressure and glass rotameter
Min, finally applies nitrogen pressure (0.5bar), casting film slurry is squeezed into spinning head (spinning head external diameter and internal diameter containing interpolation pipe
Respectively 2.5mm and 1.0mm)；The micro-pipe wet film extruded from spinning head immerses outer coagulating bath behind 1.5cm the air gap
Stood in (absolute ethyl alcohol) after 24h gelling solidifications, obtain micro-pipe film precursor；
(3) dry and high temperature sintering
Above-mentioned micro-pipe film precursor is placed in and dried at room temperature after 24h, is sintered using electron tubes type high-temperature electric resistance furnace, is burnt
Knot condition is：With 98%Ar/2%H2Mixed gas is incubated 5h as protection gas at a temperature of 1450 DEG C；Naturally cool to room
Temperature, that is, obtain graphene doping proton conductor (graphene/BaZr0.1Ce0.7Y0.2O3-δ) the fine and close micro-pipe ceramics of unsymmetric structure are thoroughly
Hydrogen film, wall thickness is 260 μm, and outside dense separation layers thickness is 30 μm.
The performance test of the embodiment of the present invention：
Using with the identical BZCY raw materials of the embodiment of the present invention one and shaping and firing process, the Ni/BZCY prepared
Biphase ceramics film (45wt% containing Ni, BZCY55wt%, or Ni 36vol%, BZCY 64vol% are expressed as with volume fraction)
As a comparison case one.With pure BaZr0.1Ce0.7Y0.2O3-δFilm as a comparison case two.
Ceramic of compact of embodiment of the present invention hydrogen permeation membrane and the Ni/BZCY biphase ceramics film of comparative example one, comparative example two is pure
BaZr0.1Ce0.7Y0.2O3-δFilm, is polished to thickness for 0.5mm, with 80%N at a temperature of 900 DEG C2/ 20%H2For unstripped gas (flow velocity
For 100mLmin-1), high-purity N2Hydrogen permeation flux is tested for scavenging；It is (in air cold to circulate chilling between 900 DEG C~25 DEG C
But) most very much not cracking cycle-index is thermal shock number, and its test result is as shown in table 1.
The performance parameter of the present embodiment of table 1 and comparative example ceramic membrane
The result of table 1 shows, compared with comparative example one, comparative example two, the hydrogen permeability of ceramic membrane of the embodiment of the present invention, power
Learn intensity and thermal shock resistance is significantly improved.
Claims (9)
- The proton conductor ceramic of compact hydrogen permeation membrane 1. a kind of high osmosis graphene adulterates, it is characterised in that：By graphene and proton Conducting oxide two-phase is constituted, the doping of the graphene is 0.03~0.25wt%, and the proton conductor oxide contains Measure as 99.75~99.97wt%.
- The proton conductor ceramic of compact hydrogen permeation membrane 2. high osmosis graphene according to claim 1 adulterates, it is characterised in that： The doping of the graphene is 0.07~0.1wt%, and the content of the proton conductor oxide is 99.90~99.93wt%.
- The proton conductor ceramic of compact hydrogen permeation membrane 3. high osmosis graphene according to claim 1 adulterates, it is characterised in that： The proton conductor oxide is perovskite structure composite oxide BaZr0.1Ce0.7Y0.2O3-δ。
- The preparation method of proton conductor ceramic of compact hydrogen permeation membrane 4. one of the claim 1-3 high osmosis graphenes adulterate, It is characterized in that：It is blended, shaping, dry using graphene or graphene oxide and proton conductor oxide powder as raw material Dry, high temperature sintering, is made graphene doping proton conductor ceramic of compact hydrogen permeation membrane.
- The preparation method of proton conductor ceramic of compact hydrogen permeation membrane 5. high osmosis graphene according to claim 4 adulterates, It is characterized in that：The graphene or graphene oxide are added in the form of dry powder or suspension；The thickness of the graphene It is 50~300nm for 0.35~1nm, piece footpath；The thickness of the graphene oxide is that 0.7~1.5nm, piece footpath are 50~300nm； The average grain diameter of the proton conductor oxide powder is 100~300nm.
- The preparation method of proton conductor ceramic of compact hydrogen permeation membrane 6. high osmosis graphene according to claim 4 adulterates, It is characterized in that：For preparing sheet symmetrical structure ceramic of compact hydrogen permeation membrane, comprise the following steps：(1) raw material is mixed withUsing the graphene or graphene oxide and proton conductor oxide powder as raw material, using zirconia ball mill, with Absolute ethyl alcohol, isopropanol or 1-METHYLPYRROLIDONE are decentralized medium, are situated between by mill of zirconia ball, in 250~300rpm of rotating speed 1~3h of lower ball milling mixing, obtains raw mixture；(2) it is dry-pressing formedThe raw mixture, which is placed in baking oven at a temperature of 70~80 DEG C, fully to be dried, through granulation it is scattered after, using dry-pressing into Type is pressed into thickness for 0.4~1mm laminar film green compact under 200~300MPa pressure；(3) dry and high temperature sinteringThe laminar film green compact carry out high temperature sintering after being dried at a temperature of 80~100 DEG C, obtain sheet symmetrical structure densification pottery Porcelain hydrogen permeation membrane.
- The preparation method of proton conductor ceramic of compact hydrogen permeation membrane 7. high osmosis graphene according to claim 4 adulterates, It is characterized in that：For preparing the fine and close micro-pipe ceramic hydrogen permeation membrane of unsymmetric structure, comprise the following steps：(1) raw material is mixed withUsing the graphene or graphene oxide and proton conductor oxide powder as raw material, add bonding agent polyether sulfone, divide Powder polyvinylpyrrolidone, using zirconia ball mill, with 1-METHYLPYRROLIDONE, dimethylformamide or dimethyl sulfoxide For solvent, zirconia ball is situated between for mill, and 6~12h of ball milling mixing, makes polyether sulfone and polyvinyl pyrrole under 200~300rpm of rotating speed Alkanone fully dissolves and is well mixed powder material, prepares casting film slurry；Casting film slurry graphene-containing or graphite oxide 55~65wt% of alkene and proton conductor hopcalite, 28~36wt% of solvent, 7~9wt% of polyether sulfone, polyvinyl pyrrole 0.3~0.5wt% of alkanone；(2) extruding spinning is moldedThe casting film slurry is added into extruding spinning shaped device, 0.5~1h is vacuumized first to remove residual bubbles, Ran Houtong Core liquid, and control the core flow velocity flowed out from spinneret inner tube to be 20~50mL/ by nitrogen pressure and glass rotameter Min, finally applies 0.3~0.7bar of nitrogen pressure, the casting film slurry is squeezed into the spinning head containing interpolation pipe；Squeezed from spinning head The micro-pipe wet film gone out, which is immersed behind 1~4cm the air gap in outer coagulating bath, to be stood after 12~24h gelling solidifications, obtains micro- Periosteum presoma；(3) dry and high temperature sinteringThe micro-pipe film precursor carries out high temperature sintering after drying, obtains the fine and close micro-pipe ceramic hydrogen permeation membrane of unsymmetric structure.
- The preparation of proton conductor ceramic of compact hydrogen permeation membrane 8. the high osmosis graphene according to claim 4 or 6 or 7 adulterates Method, it is characterised in that：The sintering condition of the high temperature sintering is 2~5h of insulation at a temperature of 1350~1500 DEG C.
- 9. the preparation side for the proton conductor ceramic of compact hydrogen permeation membrane that adulterated using one of the claim 4-8 high osmosis graphenes Product made from method.
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| CN108854928A (en) * | 2018-07-05 | 2018-11-23 | 山东理工大学 | Preparation method preparing hydrogen by ammonia decomposition reaction and separate economic benefits and social benefits ceramic of compact membrane reactor |
| CN108939944A (en) * | 2018-06-25 | 2018-12-07 | 华南理工大学 | A kind of nonmetallic ion-doped Ca-Ti ore type mixed conductor hydrogen permeation membrane and its preparation method and application |
| CN109896837A (en) * | 2019-03-29 | 2019-06-18 | 江西省康舒陶瓷有限公司 | A kind of heat-stable ceramic soup stews and preparation method thereof |
| CN110420568A (en) * | 2019-09-03 | 2019-11-08 | 北京林业大学 | A method of promoting ceramic membrane permeant flux improves strainability |
| CN111359543A (en) * | 2020-05-11 | 2020-07-03 | 信阳学院 | Metal ceramic membrane reactor for natural gas conversion |
| US10899613B2 (en) * | 2017-10-20 | 2021-01-26 | University Of South Carolina | Graphene-ceramic composite membrane for hydrogen separation membranes |
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| US10899613B2 (en) * | 2017-10-20 | 2021-01-26 | University Of South Carolina | Graphene-ceramic composite membrane for hydrogen separation membranes |
| CN108939944A (en) * | 2018-06-25 | 2018-12-07 | 华南理工大学 | A kind of nonmetallic ion-doped Ca-Ti ore type mixed conductor hydrogen permeation membrane and its preparation method and application |
| CN108939944B (en) * | 2018-06-25 | 2021-05-14 | 华南理工大学 | Non-metal ion doped perovskite type mixed conductor hydrogen permeation membrane and preparation method and application thereof |
| CN108854928A (en) * | 2018-07-05 | 2018-11-23 | 山东理工大学 | Preparation method preparing hydrogen by ammonia decomposition reaction and separate economic benefits and social benefits ceramic of compact membrane reactor |
| CN109896837A (en) * | 2019-03-29 | 2019-06-18 | 江西省康舒陶瓷有限公司 | A kind of heat-stable ceramic soup stews and preparation method thereof |
| CN110420568A (en) * | 2019-09-03 | 2019-11-08 | 北京林业大学 | A method of promoting ceramic membrane permeant flux improves strainability |
| CN110420568B (en) * | 2019-09-03 | 2022-11-29 | 北京林业大学 | Method for improving water production flux of ceramic membrane and improving filtration performance |
| CN111359543A (en) * | 2020-05-11 | 2020-07-03 | 信阳学院 | Metal ceramic membrane reactor for natural gas conversion |
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